A method for preparing B, Si-bimetallic reagent

Abstract

The invention discloses a method for preparing a B, Si bimetallic reagent, wherein an aryl-substituted trialkoxy silicon compound, a double (2,4-dimethyl-2,4-pentanediol) borate, a methoxy (cyclooctadiene) iridium dimer, and 3,4,7,8-tetramethyl-1,10-phenanthroline are sequentially added to a glass reaction tube, and cyclohexane is used as a solvent to obtain a B, Si bimetallic reagent. Various B, Si bimetallic reagents can be prepared with good to excellent yields within 30 minutes using the method of the present invention. These B, Si bimetallic reagents can be directly applied to the synthesis and modification of drug molecules and can be used for other further reactions. At the same time, the preparation method is fast and efficient, with good site selectivity; the synthetic route is safe and easy, and the cost is relatively low; traditional anhydrous and oxygen-free conditions are not required, and the reaction operation and post-processing process are simple.

Description

Technical Field

[0001] The invention relates to a method for preparing a B, Si-bimetallic reagent, and in particular to a highly efficient method for synthesizing a novel B, Si-bimetallic reagent by using double (2,4-dimethyl-2,4-pentanediol) borate as a boron source. Background Art

[0002] Suzuki-Miyaura and Hiyama cross-coupling reactions provide a reliable and convenient method for the preparation of complex drug molecules and natural products. B, Si-bimetallic reagents are very attractive as important synthons in transition metal-catalyzed cross-coupling reactions because they contain B and Si functional groups that promote selective transformations.

[0003] In the prior art, there are a few literature reports on the synthesis of B, Si-bimetallic reagents to achieve the construction of CB bonds. For example, document (1). Mark G. McLaughlin, Catherine A. McAdam, and Matthew J. Cook. MIDA–Vinylsilanes: Selective Cross-Couplings and Applications to the Synthesis of Functionalized Stilbenes. Org. Lett. 2015, 17, 10–13. (2). Yosuke Ashikari, Tomoko Kawaguchi, Kyoko Mandai, Yoko Aizawa, and Aiichiro Nagaki. A Synthetic Approach to Dimetalated Arenes Using Flow Microreactors and the Switchable Application to Chemoselective Cross-Coupling Reactions. J. Am. Chem. Soc. 2020, 142, 17039–17047. (3). Yutaro Saito, Yasutomo Segawa, Kenichiro Itami. para-C–H Borylation of Benzene Derivatives by a Bulky Iridium Catalyst. J. Am. Chem. Soc. 2015, 137, 5193–5198. (4). Yutaro Saito, Kotono Yamanoue, Yasutomo Segawa, Kenichiro Itami. Selective Transformation of Strychnine and 1,2-Disubstituted Benzenes by C–HBorylation. Chem 2020, 6, 985-993. A method for synthesizing B and Si bimetallic reagents is disclosed respectively.

[0004] The synthetic route is as follows:

[0005]

[0006] In the above technical schemes, B, Si-bimetallic reagents are traditionally prepared from (pseudo)halides, organolithium or Grignard reagents, which to some extent hinder their application because they require pre-functionalized substrates. Among all the known iridium-catalyzed para-selective CH bond borylation reactions, aryl silicon is less explored, and only three examples of para-selective CH bond borylation reactions controlled by bulky diphosphine ligands have been reported, but the site selectivity is poor (para / other <9 / 1).

[0007] Therefore, in view of the above situation, it is necessary to propose a method that is easy to synthesize, has good site selectivity, and has wide substrate adaptability to quickly and efficiently prepare B and Si bimetallic reagents to solve the above problems. Summary of the invention

[0008] The present invention aims to provide a method for preparing a B, Si bimetallic reagent.

[0009] The technical solution of the present invention is:

[0010] A method for preparing a B, Si-bimetallic reagent comprises: sequentially adding an aromatic substituted trialkoxy silicon compound, a bis(2,4-dimethyl-2,4-pentanediol) borate, a methoxy(cyclooctadiene) iridium dimer and 3,4,7,8-tetramethyl-1,10-phenanthroline into a glass reaction tube, using cyclohexane as a solvent, fixing the glass reaction tube in a heated stirrer for stirring, and after the reaction is completed, performing column chromatography separation and purification treatment on the product to obtain a novel B, Si-bimetallic reagent synthesized using the bis(2,4-dimethyl-2,4-pentanediol) borate as a boron source.

[0011] Furthermore, the aryl-substituted trialkoxy silicon compound is any one of the following two structural formulas:

[0012]

[0013] in,

[0014] R1 is any one of hydrogen, methyl, ethyl, isopropyl, cyclopropyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy;

[0015] R2 is hydrogen or methyl;

[0016] R3 is hydrogen or fluorine;

[0017] R4 is any one of hydrogen, fluorine or chlorine;

[0018] R5 is any one of hydrogen, methyl, methoxy, isopropoxy, methoxymethoxy, 1,3-dioxolan-2-yl, methoxymethyl, (3,5-dimethoxybenzyl)oxy, and (3,5-dimethylphenoxy)methyl.

[0019] Furthermore, the bis(2,4-dimethyl-2,4-pentanediol) borate compound has the following structural formula:

[0020]

[0021] Furthermore, the molar ratio of the aromatic substituted trialkoxy silicon compound, methoxy(cyclooctadiene)iridium dimer, 3,4,7,8-tetramethyl-1,10-phenanthroline and bis(2,4-dimethyl-2,4-pentanediol)borate is 1:0.015-0.030:0.030-0.060:1.5-2.0.

[0022] Furthermore, the molar ratio of the aromatic substituted trialkoxy silicon compound, methoxy(cyclooctadiene)iridium dimer, 3,4,7,8-tetramethyl-1,10-phenanthroline and bis(2,4-dimethyl-2,4-pentanediol)borate is 1:0.015:0.03:1.5.

[0023] Furthermore, the concentration of cyclohexane is 0.2 mmol / mL.

[0024] Furthermore, the rotation speed of the heating stirrer is 400-800 rpm, the heating temperature is 100° C., and the reaction time is 30 min-4 h.

[0025] Further, the reaction process is:

[0026]

[0027] Furthermore, the reaction is carried out in an air atmosphere.

[0028] Furthermore, the reaction atmosphere is N2.

[0029] The present invention provides a method for preparing a B, Si-bimetallic reagent, which has the following beneficial effects:

[0030] 1. The B and Si bimetallic reagents obtained by the method of the present invention are of various types and can be directly applied to the synthesis, modification and coupling of related drug molecules, enriching the development of the CB bonding research field and having great potential value;

[0031] 2. Compared with the traditional CH bond borylation reaction, the present invention has better para-selectivity;

[0032] 3. The reaction conditions of the present invention are simple and easy to operate, the post-processing process is simple, and there are fewer by-products;

[0033] 4. The reaction of the present invention is efficient and rapid, and the conversion can be completed basically within 30 minutes;

[0034] 5. The present invention has important practical significance for enriching the structures of some drug molecules. DETAILED DESCRIPTION

[0035] The invention provides a preparation method of a B, Si-bimetallic reagent, comprising: sequentially adding an aryl-substituted trialkoxy silicon compound, a bis(2,4-dimethyl-2,4-pentanediol) borate, a methoxy(cyclooctadiene) iridium dimer and 3,4,7,8-tetramethyl-1,10-phenanthroline into a glass reaction tube, taking cyclohexane as a solvent, reacting at 100 DEG C, fixing the glass reaction tube in a heating stirrer for stirring, and performing column chromatography separation and purification treatment on a product after the reaction is completed, so as to obtain a novel B, Si-bimetallic reagent synthesized by taking the bis(2,4-dimethyl-2,4-pentanediol) borate as a boron source.

[0036] The reaction process of the above technical solution can be expressed as:

[0037]

[0038] The column chromatography separation and purification treatment mentioned above is a conventional method for separating compounds in organic chemistry. The specific steps are: fill 200-300 silica gel directly into the chromatography column, then gently tap the sides of the column until the silica gel interface no longer drops, and then add petroleum ether to compact the chromatography column. The reaction mixture is cooled to room temperature and filtered through a small piece of diatomaceous earth, and then silica gel is added and evaporated under reduced pressure to obtain a crude product. The crude product is added to the compacted chromatography column, and a developing agent (petroleum ether: ethyl acetate = 20:1) is added for separation, and finally the target product is obtained by evaporation under reduced pressure.

[0039] In order to make the above-mentioned objects, features and advantages of the present invention more clearly understood, the technical solutions of the present invention are further described below in conjunction with embodiments. However, the present invention is not limited to the embodiments listed, and should also include any other known changes within the scope of the rights claimed by the present invention.

[0040] The term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The term "in one embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive with other embodiments.

[0041] Example 1

[0042] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: tris((2,6-dimethylheptane-4-yl)oxy)silane and bis(2,4-dimethyl-2,4-pentanediol)borate are used as raw materials, and the reaction formula is as follows:

[0043]

[0044] (1) Add tri((2,6-dimethylheptane-4-yl)oxy)silane (3.0 mmol), 0.0300 g (0.0450 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0225 g (0.0900 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 1.2690 g (4.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 10.00 mL of cyclohexane into a reaction tube, and react at 100° C. for 30 minutes under air atmosphere;

[0045] ⑵TLC tracks the reaction until it is completely completed;

[0046] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 98%).

[0047] 1 H NMR(400MHz,Chloroform-d)δ7.81(d,J=7.9Hz,2H),7.69–7.57(m,2H),4.19–4.05(m,3H) ,1.95(s,2H),1.85–1.70(m,6H),1.46(s,18H),1.33–1.27(m,6H),0.86(d,J=6.6Hz,36H). 13 C NMR (101MHz, Chloroform-d) δ136.0,134.2,132.8,70.9,69.9,49.2,47.1,32.0,24.6,23.2,22.9. 11 B NMR(128MHz,Chloroform-d)δ26.7.HRMS(ESI)m / zCalcd forC 40 H 75 BNaO5Si[M+Na] + 697.5369,Found:697.5381.

[0048] Example 2

[0049] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: tris((2,6-dimethylheptane-4-yl)oxy)(o-tolyl)silane and bis(2,4-dimethyl-2,4-pentanediol)borate are used as raw materials, and the reaction formula is as follows:

[0050]

[0051] (1) 0.1098 g (0.2 mmol) of tris((2,6-dimethylheptane-4-yl)oxy)(o-tolyl)silane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane were added to a reaction tube and reacted at 100° C. for 4 hours under air atmosphere;

[0052] ⑵TLC tracks the reaction until it is completely completed;

[0053] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 86%).

[0054] 1 H NMR(400MHz,Chloroform-d)δ7.70(d,J=7.6Hz,1H),7.60–7.58(m,2H),4.20–4.04(m,3H),2.54(s,3H) ,1.93(s,2H),1.83–1.67(m,6H),1.59–1.41(m,18H),1.37–1.26(m,6H),0.85(dd,J=6.7,2.7Hz,36H). 13 C NMR (101MHz, Chloroform-d) δ142.6,135.7,135.5,134.8,129.8,70.9,70.1,49.2,47.0,32.0,24.6,23.4,23.1,23.1. 11 B NMR(128MHz,Chloroform-d)δ26.8.HRMS(ESI)m / z Calcd for C 44 H 77 BNaO5Si[M+Na] + 711.5526,Found:711.5531.

[0055] Example 3

[0056] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: tris((2,6-dimethylhept-4-yl)oxy)(2-ethylphenyl)silane and bis(2,4-dimethyl-2,4-pentanediol)borate are used as raw materials, and the reaction formula is as follows:

[0057]

[0058] (1) 0.1126 g (0.2 mmol) of tris((2,6-dimethylheptane-4-yl)oxy)(2-ethylphenyl)silane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane were added to a reaction tube and reacted at 100° C. for 4 hours under air atmosphere;

[0059] ⑵TLC tracks the reaction until it is completely completed;

[0060] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 82%).

[0061] 1 H NMR(400MHz,Chloroform-d)δ7.74–7.67(m,2H),7.63(dd,J=7.3,1.2Hz,1H),4.20–4.02(m,3H),2.91(q,J=7. 5Hz,2H),1.95(s,2H),1.86–1.70(m,6H),1.61–1.43(m,18H),1.43–1.27(m,9H),0.88(dd,J=6.7,2.7Hz,36H). 13 C NMR (101MHz, Chloroform-d) δ149.1,135.4,135.0,133.1,129.9,70.9,70.2,49.2,47.0,32.0,31.7,29.5,24.6,23.1,16.6. 11 B NMR(128MHz,Chloroform-d)δ27.0.HRMS(ESI)m / z Calcd for C 42 H 79 BNaO5Si[M+Na] + 725.5682,Found:725.5692.

[0062] Example 4

[0063] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: tris((2,6-dimethylhept-4-yl)oxy)(2-isopropylphenyl)silane and bis(2,4-dimethyl-2,4-pentanediol)borate are used as raw materials, and the reaction formula is as follows:

[0064]

[0065] (1) Add 0.1154 g (0.2 mmol) of tris((2,6-dimethylheptane-4-yl)oxy)(2-isopropylphenyl)silane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into a reaction tube, and react at 100 ° C for 4 hours under air atmosphere;

[0066] ⑵TLC tracks the reaction until it is completely completed;

[0067] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 85%).

[0068] 1 H NMR(400MHz,Chloroform-d)δ7.75(s,1H),7.66(d,J=7.5Hz,1H),7.59(dd,J=7.4,1.2Hz,1H),4.12(p,J=6.3Hz,3H),3.44(hept,J =6.8Hz,1H),1.92(s,2H),1.82–1.67(m,6H),1.44(s,18H),1.38–1.28(m,6H),1.28(d,J=6.8Hz,6H),0.85(dd,J=6.7,3.9Hz,36H). 13 C NMR (101MHz, Chloroform-d) δ154.0,135.2,134.8,130.1,130.1,70.8,70.2,49.2,46.9,33.4,32.0,25.1,24.6,23.2,23.1. 11 B NMR(128MHz,Chloroform-d)δ26.8.HRMS(ESI)m / z Calcd for C 43 H 81 BNaO5Si[M+Na] +739.5839,Found:739.5831.

[0069] Example 5

[0070] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: tris((2,6-dimethylheptane-4-yl)oxy)(2-cyclopropylphenyl)silane and bis(2,4-dimethyl-2,4-pentanediol)borate are used as raw materials, and the reaction formula is as follows:

[0071]

[0072] (1) Add 0.1150 g (0.2 mmol) of tris((2,6-dimethylheptane-4-yl)oxy)(2-isopropylphenyl)silane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into a reaction tube, and react at 100 ° C for 4 hours under air atmosphere;

[0073] ⑵TLC tracks the reaction until it is completely completed;

[0074] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 82%).

[0075] 1 H NMR(400MHz,Chloroform-d)δ7.70(d,J=7.4Hz,1H),7.55(d,J=7.4Hz,1H),7.11(s,1H),4.14(p,J=6.3Hz,3H),2.53–2.34(m,1H),1 .91(s,2H),1.83–1.69(m,6H),1.55–1.44(m,6H),1.43(s,12H),1.38–1.27(m,6H),1.02–0.94(m,2H),0.84(dd,J=6.7,3.3Hz,38H). 13 C NMR (101MHz, Chloroform-d) δ148.3,135.4,135.2,129.5,125.8,70.7,70.0,49.1,46.8,31.9,24.5,23.0,22.9,15.4,11.3. 11B NMR(128MHz,Chloroform-d)δ26.3.HRMS(ESI)m / z Calcd for C 43 H 79 BNaO5Si[M+Na] + 737.5682,Found:737.5685.

[0076] Example 6

[0077] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: tris((2,6-dimethylheptane-4-yl)oxy)(2-methoxyphenyl)silane and bis(2,4-dimethyl-2,4-pentanediol)borate are used as raw materials, and the reaction formula is as follows:

[0078]

[0079] (1) Add 0.1130 g (0.2 mmol) of tris((2,6-dimethylheptane-4-yl)oxy)(2-methoxyphenyl)silane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into a reaction tube, and react at 100 ° C for 4 hours under air atmosphere;

[0080] ⑵TLC tracks the reaction until it is completely completed;

[0081] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 80%).

[0082] 1 H NMR(400MHz,Chloroform-d)δ7.67(d,J=7.2Hz,1H),7.40(dd,J=7.2,0.8Hz,1H),7.20(s,1H),4.19–4.00(m,3H),3. 82(s,3H),1.92(s,2H),1.73(dq,J=13.2,6.6Hz,6H),1.50–1.38(m,18H),1.28–1.21(m,6H),0.81(d,J=6.6Hz,36H). 13C NMR (101MHz, Chloroform-d) δ163.1,137.2,125.8,124.2,113.1,70.9,69.4,54.5,49.0,46.9,31.9,24.3,23.1,22.9. 11 B NMR(128MHz,Chloroform-d)δ26.2.HRMS(ESI)m / z Calcd forC 41 H 78 BO6Si[M+H] + 705.5655,Found:705.5661.

[0083] Example 7

[0084] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: tris((2,6-dimethylheptane-4-yl)oxy)(2-ethylmethoxyphenyl)silane and bis(2,4-dimethyl-2,4-pentanediol)borate are used as raw materials, and the reaction formula is as follows:

[0085]

[0086] (1) Add 0.1158 g (0.2 mmol) of tris((2,6-dimethylheptane-4-yl)oxy)(2-ethoxyphenyl)silane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into a reaction tube, and react at 100 ° C for 4 hours under air atmosphere;

[0087] ⑵TLC tracks the reaction until it is completely completed;

[0088] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 85%).

[0089] 1 H NMR(400MHz,Chloroform-d)δ7.69(d,J=7.1Hz,1H),7.40(d,J=7.1Hz,1H),7.22(s,1H),4.23–4.05(m,5 H),1.93(s,2H),1.82–1.66(m,6H),1.51–1.42(m,21H),1.36–1.19(m,6H),0.83(dd,J=6.7,2.5Hz,36H).13 C NMR (101MHz, Chloroform-d) δ162.9,137.1,125.8,125.0,114.6,71.0,69.6,63.1,49.2,47.0,32.0,24.5,23.3,23.1,15.2. 11 B NMR(128MHz,Chloroform-d)δ25.9.HRMS(ESI)m / z Calcd for C 42 H 79 BNaO6Si[M+Na] + 741.5631,Found:741.5638.

[0090] Example 8

[0091] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: tris((2,6-dimethylhept-4-yl)oxy)(2-(trifluoromethyl)phenyl)silane and bis(2,4-dimethyl-2,4-pentanediol)borate are used as raw materials, and the reaction formula is as follows:

[0092]

[0093] (1) Add 0.1158 g (0.2 mmol) of tris((2,6-dimethylhept-4-yl)oxy)(2-(trifluoromethyl)phenyl)silane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into a reaction tube, and react at 100 ° C for 30 minutes under air atmosphere;

[0094] ⑵TLC tracks the reaction until it is completely completed;

[0095] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 97%).

[0096] 1H NMR(400MHz,Chloroform-d)δ8.10(s,1H),8.04(d,J=7.6Hz,1H),7.93(d,J=7.5Hz,1H),4.12(p,J=6.4 Hz,3H),1.95(s,2H),1.87–1.65(m,6H),1.51–1.43(m,18H),1.38–1.26(m,6H),0.85(d,J=6.8Hz,36H). 13 C NMR(101MHz,Chloroform-d)δ137.1,135.6,134.6(q,J=3.5,2.5Hz),134.3(d,J=30.6Hz), 131.3(q,J=4.8Hz),125.2(d,J=273.9Hz),71.3,70.6,49.2,46.8,32.0,24.6,23.1,23.1. 19 F NMR(376MHz,Chloroform-d)δ-58.3. 11 B NMR(128MHz,Chloroform-d)δ25.4.HRMS(ESI)m / z Calcd for C 41 H 74 BF3NaO5Si[M+Na] + 765.5243,Found:765.5238.

[0097] Example 9

[0098] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: tris((2,6-dimethylhept-4-yl)oxy)(2-(trifluoromethoxy)phenyl)silane and bis(2,4-dimethyl-2,4-pentanediol)borate are used as raw materials, and the reaction formula is as follows:

[0099]

[0100] (1) Add 0.1158 g (0.2 mmol) of tris((2,6-dimethylhept-4-yl)oxy)(2-(trifluoromethoxy)phenyl)silane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into a reaction tube, and react at 100 ° C for 30 minutes under air atmosphere;

[0101] ⑵TLC tracks the reaction until it is completely completed;

[0102] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 83%).

[0103] 1 H NMR(400MHz,Chloroform-d)δ7.74(d,J=7.3Hz,1H),7.67(d,J=7.2Hz,1H),7.62(s,1H),4.16(p,J=6.4Hz, 3H),1.94(s,2H),1.82–1.65(m,6H),1.52–1.43(m,18H),1.35–1.24(m,6H),0.85(dd,J=6.6,2.2Hz,36H). 13 C NMR (101MHz, Chloroform-d) δ 154.0, 136.8, 130.6, 128.6, 120.8 (d, J = 257.3Hz), 121.5 (q, J = 16.8Hz), 71.3, 70.27, 49.2, 46.9, 31.9, 24.6, 23.1, 23.0. 19 F NMR(376MHz,Chloroform-d)δ-55.0. 11 B NMR(128MHz,Chloroform-d)δ25.9.HRMS(ESI)m / z Calcd for C 41 H 74 BF3NaO6Si[M+Na] + 781.5192,Found:781.5184.

[0104] Example 10

[0105] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: (2-((3,5-dimethoxybenzyl)oxy)phenyl)triethoxysilane and bis(2,4-dimethyl-2,4-pentanediol)borate are used as raw materials, and the reaction formula is as follows:

[0106]

[0107] (1) Add 0.0813 g (0.2 mmol) of (2-((3,5-dimethoxybenzyl)oxy)phenyl)triethoxysilane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into a reaction tube, and react at 100 ° C for 30 minutes under air atmosphere;

[0108] ⑵TLC tracks the reaction until it is completely completed;

[0109] (3) After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 5:1) to obtain the target product (yield 82%).

[0110] 1 H NMR(400MHz,Chloroform-d)δ7.68(d,J=7.2Hz,1H),7.47(dd,J=7.0,0.8Hz,1H),7.38(s,1H),6.77(d,J=2.3Hz ,2H),6.41(t,J=2.3Hz,1H),5.12(s,2H),3.92–3.74(m,12H),1.92(s,2H),1.44(s,12H),1.18(t,J=7.0Hz,9H). 13 C NMR(101MHz,Chloroform-d)δ162.92,160.87,139.94,136.90,126.36,121. 74,115.43,105.09,99.87,70.98,69.65,58.62,55.39,49.03,31.82,18.24. 11 B NMR(128MHz,Chloroform-d)δ25.1.HRMS(ESI)m / zCalcd for C 28 H 43 BNaO8Si[M+Na] + 569.2712,Found:569.2701.

[0111] Embodiment 11

[0112] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: (3,5-difluorophenyl)triethoxysilane and bis(2,4-dimethyl-2,4-pentanediol) borate are used as raw materials, and the reaction formula is as follows:

[0113]

[0114] (1) Add 0.0553 g (0.2 mmol) of (3,5-difluorophenyl)triethoxysilane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into the reaction tube, and react at 100 ° C for 30 minutes under air atmosphere;

[0115] ⑵TLC tracks the reaction until it is completely completed;

[0116] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 84%).

[0117] 1 H NMR (400MHz, Chloroform-d) δ7.18–6.81(m,2H),3.82(q,J=7.0Hz,6H),1.98(s,2H),1.45(s,12H),1.22(t,J=7.0Hz,9H). 13 C NMR(100MHz,Chloroform-d)δ166.5(d,J C-F =12.3Hz),164.0(d,J C-F =12.6Hz),136.1,122.4–113.4(m),72.4,59.0,49.1,31.7,18.3. 19 F NMR(376MHz,Chloroform-d)δ-104.1. 11 B NMR(128MHz,Chloroform-d)δ25.6.HRMS(ESI)m / z Calcd for C 19 H 31 BF2NaO5Si[M+Na] + 439.1894,Found:439.1898.

[0118] Example 12

[0119] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: (3-chloro-5-fluorophenyl)triethoxysilane and bis(2,4-dimethyl-2,4-pentanediol) borate are used as raw materials, and the reaction formula is as follows:

[0120]

[0121] (1) Add 0.0586 g (0.2 mmol) of (3,5-difluorophenyl)triethoxysilane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into the reaction tube, and react at 100 ° C for 30 minutes under air atmosphere;

[0122] ⑵TLC tracks the reaction until it is completely completed;

[0123] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 83%).

[0124] 1 H NMR (400MHz, Chloroform-d) δ7.36 (s, 1H), 7.16 (dd, J=7.6, 0.6Hz, 1H), 3.81 (q, J=7.0Hz, 6H), 2.00 (s, 2H), 1.46 (s, 12H), 1.22 (t, J=7.0Hz, 9H). 13 C NMR(100MHz,Chloroform-d)δ164.5(d,J C-F =247.1Hz),137.6(d,J C-F =10.9Hz),135.6(d,J C-F =5.3Hz),130.5(d,J C-F =3.0Hz),118.9(d,J C-F =21.9Hz),72.6,59.0,49.1,31.6,18.3. 19 F NMR(376MHz,Chloroform-d)δ-104.9. 11 B NMR(128MHz,Chloroform-d)δ24.5.HRMS(ESI)m / zCalcd for C 19 H 31 BFClNaO5Si[M+Na] + 455.1599,Found:455.1593.

[0125] Embodiment 13

[0126] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: (5-chloro-2-isopropoxyphenyl)triethoxysilane and bis(2,4-dimethyl-2,4-pentanediol) borate are used as raw materials, and the reaction formula is as follows:

[0127]

[0128] (1) Add 0.0586 g (0.2 mmol) of (5-chloro-2-isopropoxyphenyl) triethoxy, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene) iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol) borate and 1.00 mL of cyclohexane to the reaction tube, and react at 100 ° C for 30 minutes under air atmosphere;

[0129] ⑵TLC tracks the reaction until it is completely completed;

[0130] (3) After the reaction, the crude product was separated by column chromatography (petroleum ether:ethyl acetate=20:1) to obtain the target product (yield 67%).

[0131] 1 H NMR(400MHz,Chloroform-d)δ7.54(s,1H),6.95(s,1H),4.62(hept,J=6.1Hz,1H),3.82( q,J=7.0Hz,6H),1.94(s,2H),1.44(s,12H),1.33(d,J=6.1Hz,6H),1.20(t,J=7.0Hz,9H). 13 C NMR (100MHz, Chloroform-d) δ160.6,138.2,129.2,123.5,116.8,71.9,69.4,58.7,49.0,31.6,22.0,18.3. 11 B NMR(128MHz,Chloroform-d)δ26.4.HRMS(ESI)m / zCalcd for C 22 H 38 BClNaO6Si[M+Na] + 495.2111,Found:495.2118.

[0132] Embodiment 14

[0133] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: (5-chloro-2-methoxyphenyl)triethoxysilane and bis(2,4-dimethyl-2,4-pentanediol) borate are used as raw materials, and the reaction formula is as follows:

[0134]

[0135] (1) Add 0.0601 g (0.2 mmol) of (5-chloro-2-methoxyphenyl)triethoxysilane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane to the reaction tube, and react at 100 ° C for 30 minutes under air atmosphere;

[0136] ⑵TLC tracks the reaction until it is completely completed;

[0137] (3) After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 5:1) to obtain the target product (yield 85%).

[0138] 1 H NMR (400MHz, Chloroform-d) δ7.53 (s, 1H), 6.97 (s, 1H), 3.89–3.76 (m, 9H), 1.95 (s, 2H), 1.45 (s, 12H), 1.20 (t, J = 7.0Hz, 9H). 13 C NMR (100MHz, Chloroform-d) δ162.3,137.9,130.0,122.9,115.39,72.0,58.8,55.5,49.0,31.8,18.3. 11 B NMR(128MHz,Chloroform-d)δ26.7.HRMS(ESI)m / z Calcd for C 20 H 34 BClNaO6Si[M+Na] + 467.1798,Found:467.1789.

[0139] Embodiment 15

[0140] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: (2-((3,5-dimethoxybenzyl)oxy)-5-fluorophenyl)triethoxysilane and bis(2,4-dimethyl-2,4-pentanediol) borate are used as raw materials, and the reaction formula is as follows:

[0141]

[0142] (1) Add 0.0849 g (0.2 mmol) of (2-((3,5-dimethoxybenzyl)oxy)-5-fluorophenyl)triethoxysilane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into a reaction tube, and react at 100 ° C for 30 minutes under air atmosphere;

[0143] ⑵TLC tracks the reaction until it is completely completed;

[0144] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 78%).

[0145] 1 H NMR(400MHz,Chloroform-d)δ7.29(d,J=8.9Hz,1H),7.16(d,J=4.2Hz,1H),6.72(d,J=2.3Hz,2H),6.4 0(t,J=2.3Hz,1H),5.05(s,2H),3.91–3.77(m,12H),1.94(s,2H),1.44(s,12H),1.18(t,J=7.0Hz,9H). 13 C NMR(100MHz,Chloroform-d)δ161.4(d,J C-F =242.5Hz),161.0,158.9,124.5(d,J C-F =5.6Hz),124.0(d,J C-F =25.6Hz),117.3(d,J C-F =7.8Hz),105.2,99.9,71.6,70.5,58.8,55.5,49.1,31.9,18.3. 19 F NMR(376MHz,Chloroform-d)δ-115.8. 11B NMR(128MHz,Chloroform-d)δ26.0.HRMS(ESI)m / z Calcd forC 28 H 42 BFNaO8Si[M+Na] + 587.2618,Found:587.2622.

[0146] Example 16

[0147] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: (2-((3,5-dimethylphenoxy)methyl)-5-fluorophenyl)triethoxysilane and bis(2,4-dimethyl-2,4-pentanediol)borate are used as raw materials, and the reaction formula is as follows:

[0148]

[0149] (1) Add 0.0785 g (0.2 mmol) of (2-((3,5-dimethylphenoxy)methyl)-5-fluorophenyl)triethoxysilane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into a reaction tube, and react at 100 ° C for 30 minutes under air atmosphere;

[0150] ⑵TLC tracks the reaction until it is completely completed;

[0151] (3) After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain the target product (yield 89%).

[0152] 1 H NMR(400MHz,Chloroform-d)δ7.87(d,J=5.7Hz,1H),7.42(d,J=9.5Hz,1H),6.66(s,2H),6.62(s,1H) ,5.16(s,2H),3.85(q,J=7.0Hz,6H),2.31(s,6H),1.95(s,2H),1.45(s,12H),1.22(t,J=7.5Hz,9H). 13 C NMR(100MHz,Chloroform-d)δ165.9(d,J C-F =251.4Hz),159.2,139.1,138.0(d,J C-F=3.4Hz),136.6(d,J C-F =7.9Hz),134.7(d,J C-F =5.8Hz),122.9(d,J C-F =23.6Hz),122.5,112.7,71.5,69.3,58.9,49.1,31.9,21.6,18.2. 19 FNMR(376MHz,Chloroform-d)δ-107.2. 11 B NMR(128MHz,Chloroform-d)δ26.1.HRMS(ESI)m / zCalcd for C 28 H 42 BFNaO6Si[M+Na] + 555.2720,Found:555.2731.

[0153] Embodiment 17

[0154] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: (5-fluoro-2-(methoxymethoxy)phenyl)triethoxysilane and bis(2,4-dimethyl-2,4-pentanediol)borate are used as raw materials, and the reaction formula is as follows:

[0155]

[0156] (1) Add 0.0637 g (0.2 mmol) of (5-fluoro-2-(methoxymethoxy)phenyl)triethoxysilane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into the reaction tube, and react at 100 ° C for 30 minutes under air atmosphere;

[0157] ⑵TLC tracks the reaction until it is completely completed;

[0158] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 88%).

[0159] 1H NMR(400MHz,Chloroform-d)δ7.28(d,J=4.3Hz,1H),7.25(d,J=8.8Hz,1H),5.18(s,2H) ,3.85(q,J=7.0Hz,6H),3.50(s,3H),1.93(s,2H),1.43(s,12H),1.21(t,J=7.0Hz,9H). 13 C NMR(101MHz,Chloroform-d)δ161.7(d,J C-F =244.6Hz),157.6(d,J C-F =1.4Hz),124.8(d,J C-F =5.7Hz),123.6(d,J C-F =25.5Hz),119.5(d,J C-F =7.9Hz),94.9,71.6,58.8,56.2,49.1,31.8,18.3. 19 F NMR(376MHz,Chloroform-d)δ-114.9. 11 B NMR(128MHz,Chloroform-d)δ25.5.HRMS(ESI)m / z Calcd for C 21 H 36 BFNaO7Si[M+Na] + 481.2200,Found:481.2205.

[0160] Embodiment 18

[0161] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: (5-fluoro-2-(methoxymethoxy)phenyl)triethoxysilane and bis(2,4-dimethyl-2,4-pentanediol)borate are used as raw materials, and the reaction formula is as follows:

[0162]

[0163] (1) Add 0.0605 g (0.2 mmol) of (5-fluoro-2-(methoxymethoxy)phenyl)triethoxysilane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into the reaction tube, and react at 100 ° C for 30 minutes under air atmosphere;

[0164] ⑵TLC tracks the reaction until it is completely completed;

[0165] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 3:1) to obtain the target product (yield 77%).

[0166] 1 H NMR(400MHz,Chloroform-d)δ7.74(d,J=5.8Hz,1H),7.36(d,J=9.6Hz,1H),4.57(s,2H) ,3.83(q,J=7.0Hz,6H),3.41(s,3H),1.92(s,2H),1.43(s,12H),1.23(t,J=7.0Hz,9H). 13 C NMR(101MHz,Chloroform-d)δ165.7(d,J C-F =250.7Hz),139.3(d,J C-F =3.5Hz),136.0(d,J C-F =7.9Hz),134.5(d,J C-F =5.8Hz), 123.0 (d, J = 23.8Hz), 74.0, 71.46, 58.79, 58.31, 49.11, 31.87, 18.23. 19 F NMR(376MHz,Chloroform-d)δ-107.7. 11 B NMR(128MHz,Chloroform-d)δ26.31.HRMS(ESI)m / z Calcd for C 21 H 36 BFNaO6Si[M+Na] + 465.2250,Found:465.2261.

[0167] Embodiment 19

[0168] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: (2-(1,3-dioxolane-2-yl)-5-fluorophenyl)triethoxysilane and bis(2,4-dimethyl-2,4-pentanediol) borate are used as raw materials, and the reaction formula is as follows:

[0169]

[0170] (1) Add 0.0661 g (0.2 mmol) of (2-(1,3-dioxolane-2-yl)-5-fluorophenyl)triethoxysilane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into the reaction tube, and react at 100 ° C for 30 minutes under air atmosphere;

[0171] ⑵TLC tracks the reaction until it is completely completed;

[0172] (3) After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 79%).

[0173] 1 H NMR(400MHz,Chloroform-d)δ7.95(d,J=5.8Hz,1H),7.40(d,J=9.7Hz,1H),6.06(s,1H),4.18(t,J=6.9 Hz,2H),4.00(t,J=6.8Hz,2H),3.82(q,J=7.0Hz,6H),1.91(s,2H),1.41(s,12H),1.22(t,J=7.0Hz,9H). 13 C NMR(100MHz,Chloroform-d)δ166.76(d,J C-F =252.6Hz),138.4(d,J C-F =3.5Hz),135.0(d,J C-F =6.1Hz),134.4(d,J C-F =8.3Hz),122.9(d,J C-F =23.9Hz),102.8,71.4,65.4,58.9,49.1,31.9,18.2. 19 F NMR(376MHz,Chloroform-d)δ-105.1. 11 B NMR(128MHz,Chloroform-d)δ25.8.HRMS(ESI)m / z Calcd forC 22 H 36 BFNaO7Si[M+Na] + 493.2200,Found:493.2196.

[0174] Embodiment 20

[0175] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: (5-fluoro-2-methylphenyl)triethoxysilane and bis(2,4-dimethyl-2,4-pentanediol) borate are used as raw materials, and the reaction formula is as follows:

[0176]

[0177] (1) Add 0.0545 g (0.2 mmol) of (5-fluoro-2-methylphenyl)triethoxysilane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane to the reaction tube, and react at 100 ° C for 30 minutes under air atmosphere;

[0178] ⑵TLC tracks the reaction until it is completely completed;

[0179] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 87%).

[0180] 1 H NMR(400MHz,Chloroform-d)δ7.44(d,J=5.7Hz,1H),7.32(d,J=9.6Hz,1H),3.82 (q,J=7.0Hz,6H),2.45(s,3H),1.93(s,2H),1.43(s,12H),1.23(t,J=7.0Hz,9H). 13 CNMR(100MHz,Chloroform-d)δ164.62(d,J C-F =248.2Hz),138.89(d,J C-F =3.6Hz),136.91(d,J C-F =7.2Hz),134.59(d,J C-F =5.8Hz),122.81(d,J C-F =23.3Hz),71.43,58.65,49.09,31.88,21.51,18.25. 19 F NMR(376MHz,Chloroform-d)δ-111.2. 11 B NMR(128MHz,Chloroform-d)δ25.8.

[0181] HRMS(ESI)m / z Calcd for C 20 H 34 BFNaO5Si[M+Na] + 435.2145,Found:435.2154.

[0182] Embodiment 21

[0183] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: (5-fluoro-2-methoxyphenyl)triethoxysilane and bis(2,4-dimethyl-2,4-pentanediol) borate are used as raw materials, and the reaction formula is as follows:

[0184]

[0185] (1) Add 0.0577 g (0.2 mmol) of (5-fluoro-2-methoxyphenyl)triethoxysilane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into the reaction tube, and react at 100 ° C for 30 minutes under air atmosphere;

[0186] ⑵TLC tracks the reaction until it is completely completed;

[0187] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain the target product (yield 84%).

[0188] 1 H NMR (400MHz, Chloroform-d) δ7.17(d,J=8.8Hz,1H),7.01(d,J=4.1Hz,1H),3.77(q,J=6.8Hz,9H),1.86(s,2H),1.36(s,12H),1.14(t,J=7.0Hz,9H). 13 C NMR(100MHz,Chloroform-d)δ161.23(d,J C-F =243.2Hz),159.8(d,J C-F =1.2Hz),124.0(d,J C-F =5.7Hz),123.8(d,J C-F =25.5Hz),115.8(d,J C-F=7.9Hz),71.5,58.8,55.9,49.1,31.9,18.3. 19 F NMR(376MHz,Chloroform-d)δ-116.3. 11 B NMR(128MHz,Chloroform-d)δ25.9.HRMS(ESI)m / zCalcd for C 20 H 34 BFNaO6Si[M+Na] + 451.2094,Found:451.2097.

[0189] Embodiment 22

[0190] This embodiment demonstrates an efficient method for preparing a novel B, Si-bimetallic reagent according to the following steps: (2,6-dimethylphenyl)triethoxysilane and bis(2,4-dimethyl-2,4-pentanediol) borate are used as raw materials, and the reaction formula is as follows:

[0191]

[0192] (1) Add 0.0573 g (0.2 mmol) of (2,6-dimethylphenyl)triethoxysilane, 0.0020 g (0.0030 mmol) of methoxy(cyclooctadiene)iridium dimer, 0.0014 g (0.0060 mmol) of 3,4,7,8-tetramethyl-1,10-phenanthroline, 0.0850 g (1.50 mmol) of bis(2,4-dimethyl-2,4-pentanediol)borate and 1.00 mL of cyclohexane into the reaction tube, and react at 100 ° C for 30 minutes under air atmosphere;

[0193] ⑵TLC tracks the reaction until it is completely completed;

[0194] ⑶ After the reaction, the crude product was separated by column chromatography (petroleum ether: ethyl acetate = 3:1) to obtain the target product (yield 69%).

[0195] 1 H NMR (400MHz, Chloroform-d) δ7.28(s,1H),7.15(s,1H),3.89(s,3H),3.59(s,9H),2.51(s,3H),1.91(s,2H),1.43(s,12H). 13 C NMR (100MHz, Chloroform-d) δ165.0,146.3,129.3,119.2,112.1,71.0,55.8,50.6,49.1,31.9,23.2. 11B NMR(128MHz,Chloroform-d)δ25.9.HRMS(ESI)m / z Calcd for C 18 H 31 BNaO6Si[M+Na] + 405.1875,Found:405.1877.

[0196] Compared with the prior art, the beneficial effects of the present invention are as follows: the preparation method of the B, Si-bimetallic reagent of the present invention can prepare various B, Si-bimetallic reagents with good to excellent yields within 30 minutes. These B, Si-bimetallic reagents can be directly applied to the synthesis and modification of drug molecules and can also be used for other further reactions. At the same time, the preparation method is fast and efficient, with good site selectivity; the synthetic route is safe and easy, and the cost is low; the traditional anhydrous and oxygen-free conditions are not required, and the reaction operation and post-treatment process are simple. Therefore, the new B, Si-bimetallic reagent prepared by this method has great potential application value in organic synthesis.

[0197] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. B. A method for preparing a Si-bimetallic reagent, characterized in that: The method comprises: adding an aryl-substituted trialkoxy silicon compound, a double (2,4-dimethyl-2,4-pentanediol) borate, a methoxy (cyclooctadiene) iridium dimer and 3,4,7,8-tetramethyl-1,10-phenanthroline in a glass reaction tube in sequence, using cyclohexane as a solvent, fixing the glass reaction tube in a heating stirrer for stirring, and performing column chromatography separation and purification treatment on the product after the reaction is completed, so as to obtain a novel B, Si-bimetallic reagent synthesized by using the double (2,4-dimethyl-2,4-pentanediol) borate as a boron source. The aryl-substituted trialkoxy silicon compound is any one of the following two structural formulas: in, R1 is any one of hydrogen, methyl, ethyl, isopropyl, cyclopropyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy; R2 is hydrogen or methyl; R3 is hydrogen or fluorine; R4 is any one of hydrogen, fluorine or chlorine; R5 is any one of hydrogen, methyl, methoxy, isopropoxy, methoxymethoxy, 1,3-dioxolan-2-yl, methoxymethyl, (3,5-dimethoxybenzyl)oxy, and (3,5-dimethylphenoxy)methyl.

2. The method for preparing the B, Si-bimetallic reagent according to claim 1, characterized in that: The molar ratio of the aryl-substituted trialkoxy silicon compound, the methoxy(cyclooctadiene)iridium dimer, 3,4,7,8-tetramethyl-1,10-phenanthroline and the bis(2,4-dimethyl-2,4-pentanediol)borate is 1:0.015-0.030:0.030-0.060:1.5-2.

0.

3. The method for preparing the B, Si-bimetallic reagent according to claim 1, characterized in that: The molar ratio of the aryl-substituted trialkoxy silicon compound, the methoxy(cyclooctadiene)iridium dimer, 3,4,7,8-tetramethyl-1,10-phenanthroline and the bis(2,4-dimethyl-2,4-pentanediol)borate is 1:0.015:0.03:1.

5.

4. The method for preparing the B, Si-bimetallic reagent according to claim 3, characterized in that: The concentration of cyclohexane is 0.2 mmol / mL.

5. The method for preparing the B, Si-bimetallic reagent according to claim 4, characterized in that: The rotation speed of the heating stirrer is 400-800 rpm, the heating temperature is 100° C., and the reaction time is 30 min-4 h.

6. The method for preparing the B, Si-bimetallic reagent according to claim 5, characterized in that: The reaction process is:

7. The method for preparing the B, Si-bimetallic reagent according to claim 1, characterized in that: The reaction is carried out in an air atmosphere.

8. The method for preparing the B, Si-bimetallic reagent according to claim 1, characterized in that: The reaction atmosphere is N2.

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